Nitramines



Unite Milton B. Frankel, Pasadena, and Karl Klager, Monrovia, Calif., assi@ors to Aerojet-General Corporation, Azusa, Califi, a corporation of Ohio No Drawing. Filed Feb. 19, 1957, Ser. No. 641,438

16 Claims. (Cl. 260-583) This invention relates to new compositions of matter and a method for their preparation. In particular, this invention relates to nitrarnines having the general formula:

wherein A, R and R are as defined above.

The amines used as starting materials in this invention are prepared by condensing a S-geminal dinitro alcohol with an amine, as disclosed in our copending application Serial No. 578,153, filed April 13, 1956.

To more fully illustrate our invention, the following examples are presented. It is to be understood, however, that these examples are presented merely as a means of illustration and are not intended to limit the scope of the invention in any way.

EXAMPLE I Preparation of N-3,3-dinitrobatyZ-N-LZJ-trinirmethyl nitramine A solution of N-3,3-dinitrobutyl-N-2,2,2-trinitroethyl amine in acetic anhydride was added dropwise to 100% nitric acid while maintaining the temperature at 5 C. The resulting solution was poured over ice yielding a yellow oil which slowly crystallized. The solid was collected, washed with water and recrystallized from chloroform to give 16.6 gm. of a cream-colored solid. Recrystallization from chloroform yielded cream-colored crystals, M.P. 105-l07 C., with decomposition, which exhibited an impact stability of 25 cm./2 kg. The elemental analysis of the product is as follows:

Calculcated for C H N O percent C, 19.41; percent H, 2.44; percent N, 26.42. Found: percent C, 20.18; percent H, 2.53; percent N, 26.44.

The heat of combustion was calculated to be 2232 caL/gm. and was found to be 2229 cal/gm. The explosive values of this compound are as follows:

Lead Block Value 162 Ballistic Mortar Value rate Pat-6m Patented Sept. 19, 1961 2 EXAMPLE 11 Preparation of N-3,3,3-trinitr0propyl-N-2,2-dinitr0pr0py nitramine .A solution of N-3,3,3-trinitropropyl-N-2,Z-dinitropro-' pyl amine in acetic anhydride was added dropwise to 100% nitric acid while maintaining the temperature at 5 C. The resulting solution was poured on ice precipitating a cream-colored solid which was collected, washed with water and dried. Recrystallization from carbon tetrachloride yielded cream-colored plates, M.P. 109- 109.5 C., with decomposition, exhibiting an impact stability of 35 10 cm./2 kg. The elemental analysis of the product is as follows:

Calculated for C H N O percent C, 19.41; percent H,

2.44; percent N, 26.42. Found: percent C, 19.90; percent H, 2.52; percent N, 26.91.

The heat of combustion was calculated to be 2232 cal./ gm. and found to be 2298 cal./ gm. The explosive values of this compound are as follows:

Lead Block Value 162 Ballistic Mortar Value 153 7 EXAMPLE III Preparation of bis(2,2-dinitropr0pyl) nizramine In a flask fitted with a mechanical stirrer and thermometer was placed 100 ml. of 100% nitric acid. While maintaining the temperature from 5-l0 C., 100 ml. of

acetic anhydride was added dropwise. To this solution was added 7.4 gm. (0.026 mole) of bis(2,2dinitropropyl)- amine. The resulting solution was stirred for 45 minutes while maintaining the temperature at 5-10 C. It was then poured over ice precipitating a white solid which was collected, washed with water and dried. Recrystallization from methanol yielded a product having a M.P. of

187e189 C. and an impact stability of 20 crn./ 2 kg. The elemental analysis of the product is as follows:

Calculated for C6H1QN5O10: percent C, 22.09; percent H,. 3.09; percent N, 25.77. Found: percent C, 22.52; percent H, 3.14; percent N, 25.77.

EXAMPLE IV Preparation of bis(2,2-dinitroamyl) nz'iramine To a solution of 100 ml. of 100% nitric acid and 100 ml. of acetic anhydride cooled to 5 C. was added 6.2 gm. of crude bis(2,2-dinitroamyl) amine. The solution was poured on ice to precipitate a white solid. The product was collected, washed with water and dried to yield 5.8 gm. of a white solid. Recrystallization from carbon tetrachlon'de yielded a product having a M.P. of 101-103 C. The elemental analysis of the product is as follows:..

Calculated for C H N O percent C, 31.42; percent H,

4.75; percent N, 21.99. Found: percent C, 31.70; percent H, 4.85; percent N, 21.22.

EXAMPLE V Preparation of bis(2,2-dinitr0butyl) nitramine A solution of bis(2,2-dinitrobutyl) amine in acetic anhydride was added dropwise to 100% nitric acid while maintaining the temperature at 5 C. The resulting solution was poured over ice yielding a yellow oil which slowly crystallized. The solid was collected, washed with water and recrystallized from chloroform to give a cream- Y colored solid. Recrystallization from chloroform yielded 11 9. A steroid of the general formula V CHrY R R (i= 'i -z E wherein individually R is hydrogen, R is selected from the group consisting of ,S-hydroxy and B-acyloxy, and together R and R is keto, Y is selected from the group consisting of hydrogen, hydroxy and acyloxy, and Z is selected from the group consisting of hydrogen and a-hydroxy.

10. A process for preparing a steroid of the general formula C HaY HO I in mi] wherein Y is selected from the group consisting of by- 12 drogen, hydroxy and acyloxy, and Z is selected from the group consisting of hydrogen and a-hydroxy, which comprises interacting a steroid of the general formula CHQY t t5 QU References Cited in the file of this patent UNITED STATES PATENTS Reichstein Dec. 4, 1956 Sarett Apr. 16, 1957 14. The method of preparing bis(2,2-dinitropr0py1) nitramine which comprises reacting bis(2,2-din-itropropy1) amine with nitric acid.

15. The method of preparing bis(2,2-dinitro amy1) ninamine which comprises reacting bis(2,2dinitroamy1) amine with nitric acid.

16. The method of preparing bis(2,2-dinitrobutyl) ni- References Cited in the file of this patent UNITED STATES PATENTS Schenck et a1. Jan. 17, 1956 

1. AS COMPOSITIONS OF MATTER, NITRAMINES HAVING THE FORMULA:
 10. THE METHOD OF PREPARING NITRAMINES HAVING THE FORMULA: 